Process for the dehydration of fluids



w. A. scHLJLzE PROCESS FOR THE DEHYDRATION OF FLUIDS Filed Feb. 2, 1942 BOlVHVdES UELLVM iNvENToR .@itented Aug., 2Q, i944 instan wenn a. seltene, amneville, ons., assigne to Phillips lletsoleum Company, a corporation of Delaware .spaarzaam seamen; 2, rss2, sensi No. @sassi (ci. iss- 4) El Claims.

This invention relates to aniimproved process for the dehydration oiuds. More specically, this invention provides an improved method for the removal of water from gases and liquids including hydrocarbons and the like by passing the substances to be dried lthrough a bed ci solid desiccating material possessing novel properties.

it is frequently desirable and many times necessary to remove either the greater portion of water or the last traces of moisture from gases or liquids For example, the freezing troubles of the natural gas pressure systems caused by the formation of hydrates may be eliminated by removing a suicient amount of the water vapor so that the dew 'point of the gas is at least as low as the minimum temperature of `the gas at the maximum pressure. Also, it may be necessary to remove the last traces of moisture from certain organic substances as gasolines, alcohols, esters, etc., to forestall detrimental catalytic eects or other adverse eifects such as corrosion, and the lise, it is known that adsorbent materials such as bauxite, activated alumina, silica gel, and thelilre have desiccating properties, and that suchmaterials may be reactivated and reused by heating to drive out adsorbed water. `various processes have been described wherein uids to be dehydrated were passed through beds of these granuiar adsorbent desiccants to obtain a degree ci water removal depending on the adsorptive capacity of the deslccant and the maximum adsorbed water content reached prior to `renewing or reactivating the descca-nt. Such materials are often superior to solutions of inQrganic salts o: organic compounds, particularly for treating fluids which are miscible and/or reactive with aqueous solutions or which must be substantially completely dehydrated. The above mentioned adsorbents, however, have s limited capacity for water, and require, somewhat frequent reactivation, which involves heating the entire bed and sweeping out the adsorbed 'water removable at the reactivation temperature.

Thus, in order to increase the capacity of a bed oi* a desiccant-and lengthen its dehydration service,v hygroscopic salts may be added and distributed over the .adsorbent granules in such a manner that the adsorptive capacity of the desic- 'tsnt is utilized to retain the solution and/or hygirateV oi the hygroscopic salt instead of water alone'.

The limitation on the increased water capacity secured through the use oie. hysroscopic salt in this menner is determined by the capacity oi the adsorbent base material to retain the aqueous salt solution which results from the addition of water. lf the concentration of the hygroscopic salt is great enough and the water content of the incoming duid high enough, 'the accumulated.

aqueous solution may build up on the carrier in the initial increments ofthe bed to the point `Where an aqueous phase separates from the base material; Mechanical dimcultiesy are thus encountered by the formation of vthis unadsorbed aqueous solution which eventually destroy the desiccant. lilhese may include packing, channeling and disintegration 'of the granular base material and washing away of the impregnated salt. Furthermore, these edects accompanying the formation of a separable aqueous solution in the portion of the beddirst contacted by the wat eer-containing uid may occur While the `rest of the bed oi desiccant 4.' is still operating at satisfactory drying eciency, so that the calculated overall capacity oi the bed is decreased and reactivation niust be practiced at more frequent intervals.

One object of this invention is to provide a desiccant material having an increased absorptive capacity for water without forming an aqueous layer during dehydration. A further object is to provide a desiccant having an improved drying elciency.

A still further object is to provide an improved A desiccant for a continuous process for the removal oi Water from gases and liquids. Another object is to provide a process for vwater removal from uids in a bed of adsorbent material designed for maximum adsorption throughout its length.

This invention overcomes the above-mentioned dicultles and provides an improved desiccant prepared by impregnatlng a granular adsorbent material with'a hygroscopic salt in such a man ner that the. concentration of the hygroscopic salt on the adsorbent material increases in the direction of the ow'of the duid being dehydrated. The concentration of the hygroscopic salt in each increment of the bed is so regulated that when the maximum amount of water is adsorbed thereon (that is, when the water vapor pressure of the increment of the desiccant bed equals that of the passing fluid), the weight of aqueous solution formed by the salt does not exceed the adsorptive capacity of the carrier. 'The concentration of the hygroscopic salt is gradually increased in successive increments along the length of the bed in'such a manner as to correspend inversely .with the decreased water vapor pressure of the progressively drier iiuid passing throughthebed. f v

An advantage of this method of impregnation is an increased dryness of the treated iiuid obtained by true counter-ciment dehydration.

' Thus, as the water vapor pressure of the iluid decreases with the distance travelled through the bed,the nuid cornes in contact with a stronger drying agent. A further advantage is that the adsorptive capacity and the dehydration period of the bed as a whole is increased by the prevention of the formation of a separate aqueous phase before the maximum capacity of the bed is utilized. A still further advantage is that this increase in adsorptive capacity and eiiiciency is attained with no actual increase in the total amount of impregnated salt so that improved rer--v suits may be obtained at no greater cost.

So that this invention may be better understood reference will be made to the accompanying drawing which diagrammatically illustrates an apparatus that may be used in continuously applying tbe desiccant of the invention to the Y dehydration of gases. l

Referring to the drawing, A and B are` the vessels which contain the diccating material prepared in accordance with the invention. One

I vessel operates on thedrying cycle while the other chamber B. The heated gasv in passing through the desiccant bed carries oil the moisture in the form of water vapor'. 'I'his wet regeneration gas is removed through valve 8 and pipe l. '111e regeneration gas may be' residue or waste gas of suitable composition in which case the-spent gas is removed through valve 2i and vented or used as tdci. Or, a portion of,` the wet inlet gas may be verted from the main stream and used as tion gas. vInthis case, the wet gas is passed through valve 22 into the water convdenser and water separator where the greater part of the moisture in the gas is removed. The used regeneration gas is then mixedwith the main stream to the bed. When the desiccant in vessel A is'spent, the wet inlet gas is runinto the regenerated desiccant in vessel B through vpipe I andvalve Il whiletankAiscutoiiat -vaive 2. Removal of the dried gas from B is Vaccomplished through valve I I and pipe l. The wetdesiccantntankAisregeneratedbypasslng the hot'gas from the furnace through valve l, pipe 0, and valve l2 into tank'A, and then removing-the wet gas by way of valve Il and pipe 0. Piping is also provided so that regeneration can salt. The concentration of the hygrowopic salt with which each increment of the bed is impregnated is varied so that the smallest concentration is present in the increment adjacent to the entry port and the largest concentration is adiacent to the exit port of the vessel. The intermediate increments bear intermediate concen- Y trations of salt increasing in the direction of' iiuid iiow through the bed in the dehydrating cycle. v

The pressure of the inlet gas may range from atmospheric to 1000 pounds per square inch depending on the composition of the gas to be dried, being kept lower than the pressure necessary to liquefy the gas. In the case of liquids or liqueiied gases, the liquid is simply pumped into the top of the desiccating chamber and removed from the bottom at the same rate. To provide the greatest absorptive capacity, the temperature of the inlet fluid Yand the drying bed should be kept as low as possible. preferably within the range of 32 to 100 F. Higher temperatures may be used, but the efliciency and extent of dehydration is impaired thereby due to the increased vapor pressure of water in the desiccant with increasing temperature. The

temperature of the regeneration gas may range from 300 to over 600 F., depending on the desiccant employed.- The preferred range is 400 to 600 F. when using materials such as bauxite and silica gel, although lower temperatures may be used with certain synthetic alumina.

be brought about by passage of the gas upwards z Thisdehydraiiins agent in vessels 'A and B consista-.of a, hedor .granular adsorbent desiccant sabauxite arranged in a series of separated or contiguousincrements bearing a I'he adsorbent materials that can be used in this invention are preferably such natural lubstances as bauxite, fullers earth, acid clay, although excellent results are obtained at somewhat higher cost with such synthetic adsorbents as activated alumina and silica gel. 'l'hese adsorbent materials may be activated before use by calcining at temperatures of 500 to 1500 l". The granular adsorbent materials are med in suitable particle size for permitting Iiuid iiow i without excessive pressure drop even in relatively deep beds and at ow rates consistent with eili-v cient dehydration. y

The hygroscopic salts referred to are of that class which are substantially inert toward the uids treated and which have an aiiinity i'or water at the. temperature range of the drying bed. These salts can substantially be dehydrated at the temperatures used for reactivation` of the desiccant composition. Oi' these salts, the preferred one for this invention is lithium chloride bauxite impregnated with one per cent of -iithimn lchloride, a saturated solution containing one pound of lithium chloride is prepared and sprayed Aevenly' on the calcined bauxite.V The pregnatedsaltcanbeprepared. 'I'he desiccat' ing chamber Vis then prepared foruse byputtmg,

in the bottom .ofthe chamber a layer `or section of adsorbent containing the greatest ammmt or assaeoo impregnated salt. Sections of desiccant are then put over this bottom layer, each addedsection containing a smaller -amount of impregnated salt than .the one below it. The number of sections and the range of 'concentration is determined-,by the wetness of the iluid to be treated and by the extent'to which the eiiluent is to be dried.- VAlternately, the desiccant bed may be prepared by impregnating the carrier with the maximum vconcentration of hygroscopic salt to beA utilized,

andfthen preparing sectionsor increments oi' lower.; .concentration by admixing calculated quantities of untreated carrier. If desired; -fthe sections of desiccant bearing the graduated salt concentrations may be supported separately within a single vessel or placed in separate ves- Y sels arrangedior series ilow. Y

The range of salt concentrations usually employed in preparingtheimpregnated desiccants will' vary with the hygroscopic quality of the particular salt and the adsorbent power Aof the carrier. Since the preferred salts combine with large weights of water, andV the preferred adsorbents retain only from about 10 to about'30 weight` percent of aqueous solutions, the corresponding quantitiesof the salt `may range from whichv are saturated with water vapor in the range of temperatures and pressures speciiled in the operating conditions, namely 32 to 100 F. and atmospheric to 1000 pounds per square inch. The ex nt of drying can be carried to any desired le l ranging from the water content lof the -inco ing -gas Ato substantially complete vdryness. 'I'hepreferred type oil-liquid to be treated with the type of desiccant described in.thisin vention is one` that is substantially immisoible with water and from which only the last traces of; water are tobe removed.- -In` cases of liquids miscible with water, such as alcohols, the maximum amount of water should be rst removed by such means as distillation, and the like..

`To show the striking advantage of the novel desiccant composition described in this invention in allowing the maximum amount of water to be adsorbed for the production of a given dew point, the following examples will be referred to.

Example r A dehydrating reagent was prepared by impregnating 600 pounds of calcined bauxite with 48 pounds of lithium chloride. The concentrations o! lithium chloride were graduated by preparing six sections ofthe rbed containing 100 pounds of bauxite and impregnated with 3, 5, 7, 9, 1l and 13 weight per cent of lithium chloride respectively in the direction of iuid flow.

A hydrocarbon gas saturated with water vapor at fili"v F. and atmospheric' pressure (l pound of water per 1000 cubic feet of gas) was passed through the bed of desiccant at F. and a rate of 10,000 cubic feet per hour until the bed had absorbed 10 percent by weight of water.

Y layer of the reagent after only eight weight per.'

this stage. the outlet gas had a dew point o2 -88" F. at atmospheric pressure.

Whenbauxite alone was employed as the desiccant under identical conditions, the bed Vadsorbed only about 40 pounds of water before the dew point of the treated gas rose to 40 F. at atmospheric pressure.

vIn a similar test 600 pounds of bauxite wasY uniformly impregnated with 48 pounds of lithium chloride, to-Y produce an average concentration of about 1.5 weight per cent.; -When the same hydrocarbon gas was passed through this desiccant, an aqueous solution phase formed and drained from the top section of the bed after only 33 pounds of water had been adsorbed,

equivalent to only about 5 weight per cent of the bed. This causedthe test to be discontinued although the eluent gas had a dew point of about 65 F. at atmospheric pressure.

Similar results were obtained when using calcium chloride in the above-described tests instead of lithiumchloride except that the completeness of drying was somewhat less.

` Example Il Deslccant was prepared as in Example E with 'graduated concentrations of lithium v.chloride employed in the dehydration of liquid gasoline. Gasoline containing .003 per cent. water was passed through the bed at the rate of 4,000ga1- lons per hour. Fifty-dive pounds of water was Aadsorbed by the 648 pounds of desiccant-beiore moisture was detectable in the euent gaso- When desiccant. was preparedwitha uniform concentration o f'lithiun chloride and the periment was carried out with the same gasoline, only 25 pounds of water was adsorbedbelore moisture was detectable inthe efiluent gasolixl'ie.l

In this case, however, the .moisture consisted or traces of lithium chloride solution.

A.a bed'o desiccant was preparedlln tions withthe following compositions in the direction of gas iiow:y

(1) Calcined. bauxite.

(2.) Bauxiteimpregnated cent of lithium chloride. n

(3) Bauxite impregnated cent of lithium-chloride.

with ,nte weicht pri The ilrst two of the-above-listedsections were' of equal volume and amounted to 60 per cent .of. the total bed, while the third section accounted f rortheremainder.A y y The bedwas employedvin dehydrating a hydrocarbon gas with a pounds gage pressure to' reduce the dew point to 10 F. at the same pressure. The capacity oi the bedin this service was 15 weight per cent oi water when regenerated at 500 F.

The capacity of an equal volume of untreated' bauxite was about nine weight per cent. When a' desiccant uniformly impregnated with nve weight per cent of lithium chloride was used. lithium chloride solution formed and separatedin the top cent o! water had been adsorbed.

While the above described desiccant composition is-'well 'adapted to relatively complete dehydration of gases and liquids, it-may. also be used as a part of a series of dehydration treatments using -similar or different reagents. In somo cases, in order to protect an im'- At premated reagent of this type from chemical with weight'per dew pollutof F. at 150 and/or mechanical deterioration it may be desirable to precede it with a bed of solid granular material which removes dust, coke,. entrained water or alkaline treating solutions or heavy oils or tar. This guard tower may be charged with interposed ahead of the impregnated dehydrating reagent, the bauxite may be reactivated by the described means when only water or similarly removable liquids are accumulated. Y J

Further, the impregnated dehydrating agent of this invention may be followed, if desired, by other dehydrating treatments such as by passage through a bed of the untreated adsorbent, whereby somewhat lower water contents are obtainable than in the lpresence of the hygroscoplc salt. In such cases, the very low water content of the eiiiuent gas or liquid from the reagent of the present invention produces very satisfactory dehydra tion periods `for the unimpregnated adsorbent used for the ilnal treatment.

While the invention has been described with speciic reference to the preferred operating conditions and speciic materials in the exemplary operations, itwill be understood that the invention is oi' broad scope and general application and is limited only by the appended claims.

I claim: Y

1. The process for the dehydration of non-aqueous fluids containing relatively minor amounts of dissolved water which comprises passing said fluids in contact with a'solid desiccant consisting of granular adsorbent carrier having marked dehydrating properties and impregnated with minor proportions of a hygroscopic salt in such a manner that the concentration of said salt increases in the direction of iluid flow through the desiccant.

2. The process for the dehydration oi.' nonaqueous iluids containing relatively minor amounts oi dissolved water which comprises pass-A ing said'v iluids at atmospheric temperature 45 through a contact zone containing a solid adsorbent desiccant impregnated with a minor proportiomof a hygroscopic salt in such a manner-l that the concentration of said salt increases in successive increments of the sone in the direction vo! ilow of the water-containing fluid.

marked dehydrating properties and impresriatedv gassosol with a minor proportion of a hysrnloopic salt in such a manner that the concentratirm of said salt increases in the direction of iluid now, whereby a maior proportion of the water in said fluid is removed by the desiccant, discontinuing the ilow o! iluid through said desiccant, removing adsorbed water therefrom by heating to temper-anims in the range of 300 to 600 F. while passing a stream of gas to sweep out desorbed water, and then returning the regenerated desiccant to dehydrating service.

4.The process asinclaimzinwhichthe desiccant consists of bauxite imllresnlted with lithium chloride. f A

5. The process as in claim 2 in which the desiccant consists of bauxite impregnated with lithium chloride in an amount ranging from nro to 15 per cent of the carrier.

6. A desiccant composition for the dehydration of non-aqueous fluids containing minor amounts of dissolved water which comprises a solid adsorbent desiccant bed having a marked` ytendency to adsorb water and impregnated with a hygroscopic salt, said salt representing a minor' proportion of the desiccantcomposition and being added in amounts which produce an increasing salt concentration in successive increments of the desiccant composition along the length oi' the bed.

7. Aprocess for dehydrating hydrocarboniluids containing' relatively minor amounts of water which comprises passing said iluid through an elongated bed of granular adsorbent impregnated with a hygroscopic salt, the concentration of said salt gradually increasing along the length of the bed to a degree corresponding inversely with the water vapor pressure of the hydrocarbon iluid passing therethrough.

8. A process i'or dehydrating hydrocarbon fluids containing relatively? minor amounts oi' water which comprises passing said fluid through an elongated bed oi' granular adsorbent impregnated withahygrosoopicsalatheconcmtrationofsaid salt gradually increasing in successive incremmts alongthelengthoithebedtoadegreeeorrespondinginverselywiththewatervaporpressmeofthe hydrocarbon duid passing therethrough.

9. A process for dehydrating hydrocarbon iluids containingv relatively minor amounts of wa'ter which' comprises passing said fluid through an elongated bed of granular adsorbent impregnated withahygroscopic salt,theconcmtrationofsaid saltgraduallyincreasing alongthelengthotthe `minedandsoregulatedthatsuniformadsorptiou takes place thromhout the bed.

' WALTER A. BCHULZI. 

